Alkyl aryl sulfonate detergent solutions



Nov. 8, 1955 F. N. BAUMGARTNER ALKYL ARYL SULFONATE DETERGENT SOLUTIONS 2 Sheets-Sheet l Filed Feb. ll 1950 ON. Gf N;

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duri/2 Qd 1 QQ Ov@ Hum-EIL REFLac- TQMETEL L.) N vrs FYZcL'Z aumgarrzr Say @aber bg W M4 Clbbor'ae Nov. 8, 1955 2 Sheets-Sheet 2 Filed Feb. l, 1950 m22 521 Eau GNNL n0 M .EZOLJD 51:00@ QZMGMJ HUNTER. QEFLEcToMa-ral L) N -r S FJ. nell baumgarner' (Inventor United States Patenty "Olice ALKYL ARYL SULFONATE DETERGEN T SOLUTIONS F. Neil Baumgartner, Cranford, N. J., assignor to Esso Research and Engineering Company, a corporation of Delaware Application February 1, 1950, Serial No. 141,696 5 Claims. (ci. 252-161) This invention is concerned with novel detergents of the alkyl aryl sulfonate-type and particularly with products which exhibit unusually high detergency at low concentrations in hard water. More particularly this invention is concerned with compounds of the formula,

Patented Nov. 8, 1955 l 2 ether washings and the organic layerwere combined and washed successivelywith 1% sodium bisullite and dilute sodium carbonate and dried over anhydrous calcium chloride. The ether was removed by distillation and the product distilled in vacuo. The principal cut, 118 C.- 119 C./ 1.1 mm., was then treated as follows: 70 gm. of the product and 130 ml. of absolute ethyl alcohol were treated with 14 gm. of metallic sodium at such a rate as to cause gentle boiling. When all the sodium had reacted the mixture was treated with ice water, acidilied with concentrated hydrochloric acid and the organic layer removed. The acid layer was extracted with petroleum ether. The combined extracts and organic layer were washed with water and dried. Vacuum distillation of the product yielded the desired 3-phenyldodecane boiling at l22-123 C./2 mm. f

Example 2.--Preparati0n of I-phenyldodecane Laurie acid chloride was reacted with benzene and aluminum chloride to produce n-undecyl phenyl ketone. The latter was reduced with zinc amalgam to produce l-phenyldodecane.

Example 3.-Preparaton of 2-phenyld0decane The Grignard of decyl bromide was prepared and reacted with acetophenone to give 2-phenyl-2-dodecanol.

, The latter was reduced by the same method as employed in the preparation of 3-phenyldodecane according to Example 1.`

Example 4.-Preparation of 4-phenyld0decane Pelargonic acid chloride was reacted with benzene in y Ithe presence of aluminum chloride to give normal octyl group of 11 to l2 carbon atoms in which the benzene PREPARATION OF PHENYLDODECANES Example 1 .-S-phenyldodecane 3-phenyldodecane was prepared by the reduction of 3-phenyl-3-dodecanol. 3-phenyl3dodecanol was synthesized in the following manner. The Grignard of ethyl bromide was prepared by reacting ethyl bromide with ,a suspension of magnesium in boiling anhydrous ether. To 1.5 moles of ethyl magnesium bromide was added 348 gm. of capriphenone over a period of 21/2 hours. The mixture was decomposed with a HCl-water mixture and the organic layer removed. The aqueous layer was extracted with ether, the combined ether extracts and organic layer washed with water, yand dried. Distillation in vacuo yielded 234 gm. of 3-phenyl-3-dodecanol (contaminated with some S-phenyldodecene) boiling at 144- 146 C./1.5 mm.

A mixture of 195 ml. of glacial acetic acid, 11.7 gm. of red phosphorus, and 4 gm. of iodine were gently warmed in a ask until the iodine is completely dissolved. 7

phenyl ketone. The latter was reacted with normal propyl chloride in the Grignard reaction to produce 4-phenyl- 4-dodecanol which was reduced to 4-phenyldodecane by the method employed in Example l.

Example 5 .-Preparation of 5phenyldodecane n-Heptyl phenyl ketone was prepared by reacting caprylic acid chloride with benzene in the presence of aluminum chloride. The ketone was then reacted with normal butyl chloride in the Grignard reaction. The product S-phenyl-S-dodecanol was reduced to 5-phenyldodecane by the method of Example 1.

Example 6.-Preparat0n of -phenyldodecane Caproic acid chloride was reacted with benzene in the presence of aluminum chloride to produce n-amyl phenyl ketone. The latter was reacted with normal hexyl chloride in the Grignard reaction. The product 6pheuyl6 dodecanol was reduced to -phenyldodecane by the method of Example l.

SULFONATION Each of the above alkyl aryl hydrocarbons was sulfonated to produce the corresponding sulfonate. lThe method employed was identical in all instances and will be exemplied by the following sulfonation of 3-pheny1- dodecane.

About 200 ml. of liquid SO2 was transferred to a ask containing 2O gm. of 3phenyldodecane. To this mixture was addedv 6.5 gm. of stabilized S03 (Sultan B) dissolved in 2G ml. of liquid SO2. The addition required l0 minutes, stirring vigorously throughout. The SO2 was allowed to evaporate and the resultant product subjected to vacuum to remove last traces of SO2.y It was` then poured into water, iiltered,Y neutralized with caustic to a faint brilliant-yellow end point. On cooling, the sulfonate precipitated from solution and was recrystallized from water. The sulfonate could not be isolated from water in all cases. It was salted out using isopropyl alcohol and NazCOs in those instances.

LAUNDER-OMETER DATA COI1c. f )0.1 0.15 -0.2 0.3 0.4 0.5

Sodium Sulfonate of:

Distilled Wat`er l-Phenyldodecane 45 45 L5() 30 30 l 35 Z-Phenyldodecane. 40 60 60 S0 70 8U S-Phenyldodecane. 70 '80 85, S0 80 4-Phenyldode'eane f 5-Ph'enyldodecane.

Tetrapropyl benzene 240 p. p. m. Water (-Hardn 1-Phenyldorle'eane 2-Phenyldodecane 3-Pheny1dodecane 4-Phenyldodecane. -Phenyldodecane.

Tetrapropyl Benzene.

720 pl'p. m. Water (Hardnes l-Phenyldodeeane 25 35 25 30 '35 30 2-Phenyldodecane 0 0 0 5 20 50 B-Phenyldodecane l35 45 65 85 `85 95 0 5 30 60 70 5-Phenyldodecane 0 0 0 0 0 0 G-Phenyldodecane. 0 0 0 0 0 90 0 5 45 85 90 Tetrapropyl benzene 0 lLAUNDER-OMETER DATA (SOIL4 REMOVAL) Distilled Water- S-,Phenylundecane 45 65 90 70 85 85 "li-Phenylundecane 5 v 20 50 485 `80 80 3-Phenyltridecane 70 75 80 90 90 85 4-Phenyltridecane 10 75 80 75 `85 85 240 p, p. In. Water (Hardness)- S-Phenylundecane 70 80 100 95 100 105 4-Phenylundecane 35 60 75 100 90 95 3-Pheny1tridecane 40 60 85 85 115 100 4-Phenyltridecane 10 `10 l70 95 85 105 720p. p. m. Water (Hardness)- 3-Phenylundecane 70 -Phenylundecane. 0 3-Phenyltridecane 10 25 20 65 85 95 4-Phenyltridecane 0 1 Insoluble. Concentration expressedas gin/100 mir-40% active material. S011 removal relative to-Dreft 0.5 in 240 p. p. m. H2O.

Table Il shows'the results of reilectance testernploying the Hunter multipurpose reflectometer.

Table Il LAUNDER-OMETERY VALUATION (Brightness) 24o P. P. M. HARD WATER CODCJ 0 .04 .06 .08 .12 .16 .2O

Sodium Sulonate of:

-phenyldodeeane Tetrapropyl benze 720 P. P. M. HARD WATER l-phenyldodecane 15 17 18 17 18 18 17 Z-Phenyldodeeane 15 15 16 15 17 20 20 B-phenylundecane 15 21 22 23 23 23 24 B-phenyldodeeane 15 19 20 22 24 24 26 3phenyltridecane 15 1G 17 17 20 22 23 4phenylundeeane 15 15 16 18 20 21 23 4-phenyldodecane 15 15 15 16 18 21 22 4phenyltridecane 15 16 15 16 15 18 20 5-phenyldodeeane 15 15 6-phenyldodecane 15 15 13 13 14 14 14 Tetrapropyl benzene 15 15 16 17 21 24 25 1 Concentration-percent active ingredients.

The superiority of the ysalts of :-phenyldodecane and 3-phenylundecane are shown more graphically in Figures 1 and 2.

Figure 1 represents Launder-Ometer data according to the Hunter reflectometer measurements of each of the compounds evaluatedin 240 p. 'p. m. hardness water, while Figure 2 shows the evaluation of the same compounds in 720 p. p. In. `hardness water. Examination'of each iigurerapidly reveals the superior detergency of -phenylundecane and V'3-pher1yldo'decane sodium sullonates which is reilected in the curves A and B respectively on each of the drawings. While these compounds are superior in the lower concentrations they lose none of their eiectiveness at the higher concentrations, wherein all detergents tend to become equalized.

Although the invention has"been described with respect to the sodium sulfonates of the respective alkyl aryl hydrocarbons, it is equally applicable to the other alkali metal salts thereof, namely, potassium, lithium and ammonium sulfo'nates' respectively.

Having -described the invention in the manner such that it may be practiced by those skilled in the art, what is claimed is:

'1. An vaqueous'detergent solution consisting essentially ofw'aterand :04% ofthe sodium salt of a monosulfonated benzene to one position of which vis attached the third carbon atom of' a'straight 'chain alkyl radical containing 11`to 12 carbon atoms.

'2. Aldet'er'gent solution'accor'ding' to claim l wherein the sulfonate'd benzene is 3lphenyldodecane.

V3. A"det`ergent"solution according to claim 1 wherein the sulfonated benzene is 3-phen'ylundecane.

4. A 'detergen't'solution 'according'to claim 1 wherein the wateri'has a' hardness of 240 partsper million.

`5. 2Adeter'gent solution .according to claim 2` wherein the water has a hardness of 240 parts per million.

References Cited in the le of this patent vUllITED vSTATES PATENTS yOTHER REFERENCES Gilman'et al.:'^l'ourn"al`of Organic Chemistry, vol. 8, pages V126-146 (1943). ((opy' available in U."S.'"Patent Library, Washington, DTC.) Pages 142 and 143 relied upon. 

1. AN AQUEOUS DETERGENT SOLUTION CONSISTING ESSENTIALLY OF WATER AND .04% OF THE SODIUM SALT OF A MONOSULFONATED BENZENE TO ONE POSITION OF WHICH IS ATTACHED THE THIRD CARBON ATOM OF A STRAIGHT CHAIN ALKYL RADICAL CONTAINING 11 TO 12 CARBON ATOMS. 